Di-(n-methane sulfonates) of diarylalkylene-diamines and their use for inhibiting acid-fading



- containing oxidesof nitrogen and sulfur.

Patented Feb. 13, 1 951 ALKYLENE-DIAMINES AND THEIR USE FOR INHIBITING ACID-FADING Donovan Erb Kvalnes, Penns Grove, N. 3., and

Carlton Webster Croco, Swarthmore, Pa, as- .signors to E. I. du -Pont de Nemoui's & Company, Wilmington, Del, a corporation of Dela- Ware No Drawing. Application February 24, 1950, Serial No. 146,158

4 Claims.

This invention relates to novel organic compounds. More-particularly thisinvention deals withwater-soluble di-(N-methane sulfonates) of diarylalkylene-diamines.

' 'It is an object of this invention to produce novel organic compounds useful as treating agents for textile fiber. A more specific object of this invention is to provide new agents for treatment of cellulose ester fiber in conjunction with the dyeing thereof, to render the dyeing stable against .aci'd fume-fading. Additional, important objects of this invention will appear as the description proceeds.

It .is known that materials consisting of or containing dyed cellulose acetate fibers tend to fade when they are exposed to an atmosphere This is often referred to as acidor gas-fume fading. This tendencyis more troublesome because those parts of the cellulose acetate which are more directly exposed to fumes, e. g., the edges of a roll of cellulose acetate fabric, are more discolored than the interior areas. It so happens that storage houses wherein textile fabrics are stored in the course of commercial Jobbing and distribution are commonly warmed in the winter by means of illuminating gas. The combustion products of the latter feed into the atmosphere oxides of nitrogen and sulfur, and thus produce exactly those con it ons which are injurious to dyed cellulose acetate. The problem of -gasfume fading is thus one of great commercial significance.

It has been proposed in the art to treat cellulose ester fiber with special agents which will retard or inhibit the mentioned fading. Two types of materials have been suggested or actually used for this purpose:

-1. Water-soluble agents-These may be ap plied readily from aqueous solution after dyeing. 'I'heysulfer, however, from the drawback of being readily washed out of the fiber. For this reason it is not practical to apply them to the fabric ,prior'to dyeing or during the dyeing operation, inasmuch as the latter is generally followed by a soaping and rinsing step, which would obviously remove the inhibitor.

Furthermore, when the fabric is "made into clothes the latter will upon laundering lose the inhibitor and become susceptible to gas-fume fading. I V

In-additiongthe customary water-soluble agents jl ave "thepeculiar property of reducing the light fastness of viscose fiber when dyed with direct colors. Consequently, the inhibitors cannot be applied to a combination fabric made up of cellulose ester and viscose fibers.

2. Water-insoluble agents.These must be ape. plied either from organic solvent solution .or in the form of an aqueous suspension. Both of these methods, however, are burdensome and uneconomical'. The solvent method generally entails health and fire hazards, due to the toxicity and flammability of the solvent, and often the solution is not stable so that the results obtained therewith are not consistently reproducible. "The dispersion method is troublesome in that it is difficult to get uniform dispersions and a uniform application of the agent to the fiber.

Now according to our invention, new chemical compounds are provided which not only have the useful property of inhibiting gas-fume fading of dyed cellulose acetate, but have the further admirable quality of being water-soluble in substance, but becoming converted into a Water-insoluble form on the fiber. Our novel agents therefore are applicable from an aqueous solution, but are wash fast, and may .be applied to the fabric either before dyeing, after dyeing or as an adjuvant directly into the dye bath. In addition, our new compounds seem to have little or no effect on the light fastness of direct dyes,

and therefore may be applied also to union fabrics containing, beside cellulose acetate, cotton or viscose fiber.

The novel compounds of this invention may be expressed by the general formula wherein R stands for hydrogen or methyl, RI stands for hydrogen or methyl, n is an integer not greater'than 2, while M designates a cation which dissolve readily in cold water; but when the, aqueous solution thereof is heated, they are decomposed slowly to yield water-insoluble products, wherein the central alkylene radical and the two adjacent N-atoms are probably involved in an imidazolidine or a hexahydro-1,3-diazine ring. This conversion may be illustrated by the following typical equation:

031 on V C -1y drrz-soaNa-x-uensoa Without limiting our invention the following examples are given to illustrate our preferred mode of operation. Parts mentioned are by weight.

Example 1.-Disodium salt of di-(N-methane sufonate) of N,N'-diphenyl-ethylenediamine 218 parts of sodium bisulfite were dissolved in 312 parts of water, 172 parts of 37% formaldehyde were added, and the resulting solution was held at 60 C.-65 C. for 30 minutes. The warm solution was then added to a solution of 212 parts of N,N-diphenyl-ethylenediamine in 450 parts of 95% ethyl alcohol, and the charge was agitated at 65 to 70 C. for 4 hours. The reaction mass was allowed to cool to room temperature while agitating, and then the product was filtered off and washed with about 160 parts of alcohol. The cake was slurried with about 400 parts of benzene, then filtered off and dried. It consisted of a White solid, soluble in water.. It had no definite melting point but charred when heated to a high temperature. Analysis showed it to be a tetrahydrate and to contain 1 atom of sulfur for each N-atom. Its structure, accordingly, corresponds most probably to the following formula:

mo s-H, CH -S0 Na] 411,0

C @H5NCH2 CH2NC 5155 This product may be used for the purpose of this invention, directly or after dehydration. In water, the compound decomposes gradually to yield 1,3-diphenyl-imidazolidine (see equation" Exam le 2.--Di-potassium salt of di- (N-methanesulfonate) N,N-diphenyl-ethylenediamine 56 parts of potassium pyrosulfite were dissolved in '78 parts of water, and 42 parts of 37% formaldehyde were added. This solution was then added to 53 parts of N,N'-diphenyl-ethy1enediamine dissolved in 112 parts of 95% ethyl alcohol. This mixture was agitated and heated at 65 to 70 C. for 3 hours. The charge after cooling was filtered. The filter cake was slurried with 160 parts of benzene on a steam bath, filtered hot, and dried. The product was a white powder, soluble in water. It had no definite melting point but charred at a high temperature. The product forms solid hydrates; in anhydrous form it is represented by the probable formula:

The product is similar in properties to that of Example 1, and may be-used in the same manner and for the same purpose as the product of Example 1.

Example 3.Magnesium salt of di-(N-methane sulfonate) of N,N-diphenyl-ethylenediamine 22 parts of magnesium oxide were suspended in 156 parts of water, and sulfur dioxide was passed into the suspension until 70 parts had been adsorbed, the magnesium oxide going into solution. 81 parts of 37% formaldehyde solution were then added. This solution was added to a solution of 106 parts of NN-diphenyl-ethylenediamine in 225 parts of 95% ethyl alcohol. This mixture was agitated and heated at 65 to 70 C. for 3 hours. After cooling, the product was filtered off. The product was slurried with hot benzene and filtered. Analysis showed the product to contain 1 atom of sulfur for each atom of nitrogen.

It is soluble in water, and its structure, in dehydrated state, probably corresponds to the for mula Heat, acids and alkalis accelerate the r against fume fading, in the same manner as the products of Examples 1 and 2.

Example 4.Disodium salt of di-(N-methane suljonate of N,N-dz'- (m-tolyl) -ethylenediamine 55 parts of sodium bisulfite were dissolved in 73 parts of water; 41 parts of 37% formaldehyde were added, and the mass was held at C. to C. for 30 minutes. This solution was added to a solution of 60 parts of N,N'-di-m-tolyl ethylenediamine in 130 parts of 95% ethyl alcohol.

The mixture was agitated and heated at 65 C. to C. for 3 hours. After cooling, the product was filtered off, slurried with hot benzene, filtered and dried.

The above product can be used in the dyeing.

procedure for cellulose acetate, giving good protection against fading by gas fumes. During the hydrolysis in the dyebath, the major portion is.

converted to 1,3 di-(m-tolyl) imidazolidine, while a minor portion regenerates N,N'-di-(mtolyl) -ethylenediamine.

Example 5.Dz'sodium salt of di-(N-methane sul-- ,fonate of N,N'-cZi-p-tolyl ethylenediamine 12 parts of sodium bisulfite were dissolved in 16 parts of water, -3 parts of 37% formaldehyde were added, and the mass washeld at 60 C. to."

65 C. for 30 minutes. The solution was then added to 12 parts of N,N'-di-p-tolyl ethylenediamine dissolved in 48 parts of alcohol. The

minutes) was addedto a solution 'of 212 parts of iN',-'N'--diphenyl *trimethylenediamine in 200 parts .o'f'951% ethyl alcohol. "This mixture was agitated andheated .a't'BS" C. for about 2 "hours. After cooling "to "room "temperature, the product was filtered off and the cake washed with alcohol.

Thecakewas then -slurried with 120 parts "of hot benzene, 'filtere'dand dried. Analysis showed the product to containfl -atomof sulfur'for each atom .of nitrogen. It was soluble in water and was similarinsproperties to the product of Example 1,

including the power .to protect dyes on cellulose acetate against fume-.fading.

. sutfonate) :of iN,N'-dzphenyl-.1gzepmpylenedi- 3 Famine .A solution of formaldehyde-sodium bisulfite iprepared by dissolving 43 parts of sodium .bisulfite in 62 parts of water and adding 323 parts of 35.1% formaldehyde) was added to "a solution of 45.2 "parts of N,N-diphenyl-'1,2-propyl diamine in 7.2 parts of ethyl alcohol. This mixture was agitated andheated at .65" C. to 70 C. for 4 hours. After cooling to room temperature, the

solid material .was filtered oif .and washed with 40 alcohol. It was slurried with hot benzene and filtered. The product was awhite solid, soluble in water. It is comparable as an anti-fume agent .to the product .in Example .1.

.In .a similar :manner the omega sulfonates of NNdiphenyl-1;3-.diamino butane, of N,N'-di- .tolyl alkylene diamines, and of various other N,'N'--.diaryl-alk-ylene diamines may be .readily prepared. of chief interest in our present in- .ventionare those compounds which are capable of hydrolytio decomposition .under the influence of ,heat, acids or .alkalis to produce water-insoluble decomposition products. Those that have the general formula hereinabove set forth are especially valuable, because their hydrolytic decomposition produces chiefiy a 'heterocyclic :ring product, that .is an imidazolidine or a hexahydrollfi-diazine, which are characterized by good stability :and water-insolubility. iAddition 10f formaldehyde to the aqueous treatment bath :aids on in directing the rhydmlytie.clecomposition toward production chieflyofsaidheterocyclio ring products, and suppresses the formation of other water-insoluble 'byeproducts.

It will be understood that the details of proto More maybevaried widely within the skill of those engaged in this art. Thus, "in lieu of the sodium, potassium vor magnesium formaldehyde an ralcohol-ethyleneoxide :condensation :product, poly ly eryl :ricinoleate, cetyl *trimethylammoniumlbromidaetc.

The order .of adding the reactants may 'be varied. .Forinstance, the :solution of .the :diamine may Jae added to "the .formaldehyde-bisulfite solution; the :sulfite solutions may be :added to the alcohol rsolution vof the amine followed by the formaldehyde; tor the formaldehyde may .beJadded o and then the bisulfite.

"The reactants may be mixed cold and then heated :or they ;may be mixed warm. "@Ihetempera'ture :a't which' the .reactionis carried outmay vary widely :(e. .g., :51) C. to iCJ, but the time will ibe :longer lower temperatures employed.

Other solvents :besides benzene may be IISBd to wash out unreacted material, such as acetone, carbon tetrachloride, etc.

As already mentioned, :our .novel compounds may 'beapplied to cellulose 'a'cetate material either beforedyeing,rduringrdyeing or as an after-treatmerit. For developing the inhibitor on fthefiber, any regular steaming or 'b'oiling-oif operation of the fiber may be taken advantage of, or aspecial steaming operation may be inserted. O-ur novel inhibitors may also be entered into the printing paste, where a printing process is resorted to, or they may be added to cellulose acetate :rayon B filaments.

The quantity to be applied will depend on the sensitivity of the dye to gas fumes and on the strength of 'the dyeing, the heavier shades generally requiring a greater degree of protection. But usually this quantity will be between -0i5'% and 3% based on the weight ofthe dry cellulose acetate. In such limitedquan'titi'es, *the-eifect on the light fastness of direct colors is negligibla and consequently :our novel agents may be employed safely in the dyeing of combination fabrics such as acetate and viscose or acetate and cotton.

The following additional examples will .illustrate .the mode of application of ournovel compounds, it being however understood that nolimi-.

tationis intended thereby.

cc. of warm water (100 F.) was then added, :and-

the mixture was further diluted to a volume of 1 liter. A 20 gram piece of wet, previously scoured cellulose acetate satin was then entered; and dyeingwas effected in the usual manner at to for .one hour. The cloth wasthenrinsed with warm wateran'd dried.

.A similar piece .of fabricwa's .dyediinarsimilarj bath excepttha't' no anti-fume agent was added;

When tested for atmospheric fading .loystand ard methods, the fabric treated with our .novel agent rated a color-fastness classification of 3 to 4 (good to very good), while the other sample rated =0 to '1 (very poor to poor).

Example 9.-Applicaiz'on 'prior to dyeing .A heavy-weight, .highly delustered, all-cellube 11866. which gives a water-soluble N-methane YQ'lo'se-acetate fabric'known in the trade as".taffe'ta;

su'lfonate.

run in water, using an emulsifying agent suchas '75 in 'greige condition as it .comes from "the weaving operationwas"impregnated by'theprocessknown as padding, with a solution in water containing per gallon, "'75 to 100 grams of our novel antifume agent (Example 1) andllf25 to 1 '02. are

dispersing agent (same as in Example 8) with the temperature of this liquor adjusted to between 100 and 120 F. Following padding, the cloth was passed between rolls set to permit the cloth to retain between 80% and 100% of its dry weight of the liquor, and then it was permitted to stand in the form of loosely-wound rolls for two hours at room temperature. Substantive fixation was then effected on the jig in the usual boil-off or scouring operation prior to the dyeing operation. this step consisting of treatment for 50 to 60 minutes at 160 to 200 F. in a water liquor con-'- taining per liter 2 to 4 grams of Duponol D paste (the aforementioned dispersing agent), 1 to 2 grams of soap and 0.75 to 1.25 grams of trisodium phosphate. Following the usual rinsings in water, the cloth was next dyed by conventional methods.

An additional quantity of the inhibitor (0.5 to 1% by weight based on the dry weight of the cloth) may be added to the dye bath, if desired.

Fabrics processed with the inhibitor by this procedure exhibit good resistance to atmospheric fading when subjected to the A. A. T. C. C. test method.

Example 10.-Applz'catio1i in a printing process Printing pastes of the following composition were prepared:

Paste A B Parts Parts 1,4-diamino-2-methoxyanthraquinone 0. 25 0. Glycerine 5 Water. 40 35 Textile G 55 55 Anti-Fume Agent (Example 1) None 5 Ercmple 11.-Applz'cation in a continuous process Pad liquors of the following compositions were prepared:

Part Parts 4-an1ino4 :nitroazobenzene 2. 5 2. 5 4-nitro'4-(ethy1, hydroxyethylamino) azobenzena. 5 5v The blue dye of Example IX. U. S. P. 2,050,704.. 5 5 Anti-.Fume'agent (Examplel) None 40 Duponol Dpaste (same dispersing agent asin Example 8) 1 l Water. 986. 5 946. 5

The temperature of these liquors was adjusted to 180 andseparate pieces of an all-cellulose-acetate rayon satin were saturated with them by the padding process and then passed between rolls with apressure to permit the cloth to retain about 70% of its dry weight of these liquors. In a continuous sequence, each cloth was then passed through another liquor known; as the booster bath e dwhi b con ained: 1

Parts Parts Pad liquor from above 2 Anti-Fume Agent (Example 1) 2 Water. 98 96 Tnfal 10o 100 the temperature of the booster liquor being adjusted to 212 F., (the boiling temperature i' water). Under this condition, steam was formed above the surface of the booster liquor and this steam being confined within an enclosed; area served to fix substantively, both dye and inhibitor. The time of passage through the booster liquor and confined steam area may be adjusted as ex; pedient. In this experiment, it was one minute, and was followed by rinsing the cloth in warm water and then drying.

When subjected to the A. A. T. C. C. test .for fastness to atmospheric fading, the cloth treated in the B liquors exhibited much better fastness than the cloth treated in the A liquors.

Numerous other ways for applying our novel products are available and will readily suggestthemselves to those skilled .in the art. Thus, formaldehyde may be added to the treatment bath in optional quantity, say up to 1 mole for-each mole of inhibitoremployed, to aid in the hydrolysis of the inhibitor into imidazoline type compounds. Other details of our examples may likewise be varied without departing from the spirit of this invention. 1

We claim as our invention:

1. A compound of the general formula wherein R designates a member of the group consisting of hydrogen and methyl, R designatesa member of the group consisting of hydrogen and methyl, M is a cation which does not renderjthe compound insoluble in water, and n is an integer not greater than 2. I

2. The di(a1kali-metal) salt of di-(N-methane sulfonate) of N,N'-dipheny1-ethylenediamine. ,y l

3. The di(alkali-metal) salt of di-(N-methane sulfonate) of N,1 l'-diphenyl-1,2-propylene di amine.

4. A process for improving the colorfastness of dyed cellulose ester fiber against acid-fume fading, which comprises treating said fiber with an aqueous solution of a compound as defined in claim 1, and then exposing the fiber to heat', to insolubilize the compound on the fiber.

DONOVAN ERB KVALNES. CARLTON WEBSTER on'oco.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,388,816 Bean L Nov." 13', 1945 2,416,380 Collie T'eb. 5. i947 

1. A COMPOUND OF THE GENERAL FORMULA 